EP0023671B1 - Verfahren zur Herstellung kationischer Farbstoffe - Google Patents

Verfahren zur Herstellung kationischer Farbstoffe Download PDF

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Publication number
EP0023671B1
EP0023671B1 EP80104329A EP80104329A EP0023671B1 EP 0023671 B1 EP0023671 B1 EP 0023671B1 EP 80104329 A EP80104329 A EP 80104329A EP 80104329 A EP80104329 A EP 80104329A EP 0023671 B1 EP0023671 B1 EP 0023671B1
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EP
European Patent Office
Prior art keywords
water
process according
mixture
reaction
chlorinated hydrocarbon
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Expired
Application number
EP80104329A
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German (de)
English (en)
French (fr)
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EP0023671A1 (de
Inventor
Klaus-Friedrich Dr. Lehment
Roderich Dr. Raue
Harald Dr. Gleinig
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Bayer AG
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Bayer AG
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Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0023671A1 publication Critical patent/EP0023671A1/de
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B44/00—Azo dyes containing onium groups
    • C09B44/005—Special process features in the quaternization reaction
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B26/00—Hydrazone dyes; Triazene dyes
    • C09B26/02—Hydrazone dyes
    • C09B26/04—Hydrazone dyes cationic

Definitions

  • DE-C-1 770782 methylates these color bases in the presence of special tertiary ones Amines described, with anhydrous organic solvents being used in all examples.
  • DE-A-2 509 622 discloses a process for the preparation of cationic hydrazone dyes by quaternizing azobases with dimethyl sulfate in solution and in the presence of an acid-binding agent, which is characterized by the use of a dimethyl sulfate shot of 100-300% per mole of intermediate, by using an aqueous solution with at least 30% water as the reaction medium and by using 2.0-3.5 mol of magnesium oxide per mole of intermediate.
  • a characteristic feature of this process is an extremely high excess of dimethyl sulfate and a correspondingly high use of magnesium oxide as an acid-binding agent.
  • the description also shows that the process is carried out at temperatures between 70 and 120 ° C.
  • Suitable solvents include benzene, toluene, xylene, o-dichlorobenzene and monochlorobenzene.
  • the saponification products of the excess dimethyl sulfate represent a waste water pollution, which is why a process is desired in which the excess of dimethyl sulfate can be kept as low as possible.
  • the corresponding color salts for example hydrochlorides, sulfates or nitrates, can also be used.
  • the amount of acid-binding agent must then be calculated so that the color salt is first converted to the base, since only the color base is accessible to methylation.
  • the chlorinated hydrocarbons are used in a weight ratio of 2: 1 to 0.3: 1.
  • acid-binding agents sodium hydroxide, sodium carbonate, potassium hydroxide and potassium carbonate. With these acid-binding agents, it is advantageous to use a metering device which is controlled by a pH meter.
  • the methylation is complete when the azobase content, based on the methylated end product, is below 0.5%.
  • the dye can be salted out and isolated in a conventional manner after removal of the chlorinated hydrocarbon by steam distillation; however, the dye solution can also be evaporated to dryness with or without removal of the chlorinated hydrocarbon in a vacuum paddle dryer or in a spray dryer. This process has the advantage that no waste water is produced.
  • the aromatic and especially the aliphatic chlorinated hydrocarbons have a high solubility for the hydrates of the methosulfates of the cationic hydrazone dyes.
  • the cationic hydrazone dye is therefore separated off in the organic phase and the organic phase is evaporated in vacuo.
  • 1,2-dichloropropane is a particularly suitable solvent for this process.
  • an azo salt obtained by coupling to 2,3,3-trimethyl-indolenine is used as the starting compound and the methylation is carried out in 2 stages.
  • the water phase becomes , which contains practically only inorganic salts.
  • the remaining organic phase preferably containing 5-15% water, is treated with 1.3-1.9 mol of dimethyl sulfate at 20-60 ° C.
  • the organic phase is evaporated to give a dye of excellent quality.
  • a particularly low excess of dimethyl sulfate is sufficient if the conversion of the azo salts obtained by coupling to 2,3,3-trimethyl-indolenine to the corresponding hydrazone dyes is carried out as follows:
  • the azo salt is used in a mixture of chlorinated hydrocarbon and water and with neutralized the equivalent amount of an alkali hydroxide or carbonate solution at 40-60 ° C.
  • the conversion of the azo salt, which is sparingly soluble in both media, to the free base takes place quickly and quantitatively. Separation of the aqueous salt solution gives the solution of the azobase in the chlorinated hydrocarbon.
  • An acid-binding agent is added to this solution and the methylation is then carried out at 35-60 ° C.
  • the dyes produced in this way are distinguished by an extremely low content of unmethylated azo color base; it is always less than 0.5%, in most cases 0.1-0.2%. Dyes of this purity are particularly suitable for dyeing polyacrylonitrile in brilliant, lightfast shades from greenish yellow to golden yellow.
  • color bases which are obtained by coupling 4-anisidine to 1,3,3,5-tetramethyl-2-methylene-indoline, 5-chloro-1,3,3- trimethyl-2-methylene-indoline, 5-methoxy-1,3,3-trimethyl-2-methylene-indoline or 5-ethoxy-1,3,3-trimethyl-2-methylene-indoline, and otherwise proceeds in the same way Wise, valuable cationic hydrazone dyes are also obtained.
  • azobases instead of the azobase used here, equimolecular amounts of the azobases from diazotized 4-toluidine and 5-chloro-1,3,3-trimethyl-2-methylene-indoline, 5-methoxy-1,3,3-trimethyl-2-methylene are used -Indoline, 7-methoxy-1,3,3-trimethyl-2-methylene-indoline and 5-chloro-7-methoxy-1,3,3-trimethyl-2-methylene-indoline and the procedure is otherwise the same, see above valuable cationic hydrazone dyes are also obtained.
  • the intermediate which is obtained by coupling diazotized 4-anisidine to 1,3,3-trimethyl-2-methylene-indoline and converting it to the azobase, are mixed with 240 g of water and 250 g of 1,2-dichloropropane stirred at room temperature. 12 g of basic magnesium carbonate are then added, and 90 g of dimethyl sulfate are then allowed to flow in. After an induction phase of 30-60 min at 20-25 ° C, the reaction begins, whereby the yellow precursor changes color to red due to the gradually developing dye. During the subsequent approx. 1 hour exothermic reaction phase, the temperature is kept at 23-25 ° C by careful water cooling.
  • the reaction mixture becomes thin. After the exothermic reaction has subsided, the mixture is subsequently stirred at 20-25 ° C. for about 15 hours, then heated to 60 ° C. in 4 hours and stirred at 60 ° C. for 1 hour. The residues of dimethyl sulfate are rapidly hydrolyzed at 60.degree. The preliminary product content is now determined by thin layer chromatography, it is below 0.2%.
  • the pH is 6-6.5. By adding 10-15 ml of 30% hydrochloric acid, the pH is adjusted to 2-3 and 1,2-dichloropropane is distilled off with steam.
  • the dye is now salted out with sodium chloride, after stirring for several hours the dye suspension is adjusted to pH 5, the dye is suctioned off and washed with 750 ml of 7% sodium chloride solution and dried in vacuo to a residual moisture content of less than 4%. Yield: 186 g of cationic hydrazone dye, precursor content: 0.1%.
  • precursors which are obtained by coupling diazotized aniline, 4-toluidine or 3-chloro-4-anisidine to 1,3,3-trimethyl-2-methylene-indoline and converting them to the color base, and otherwise proceeds in the same way, valuable cationic hydrazone dyes are also obtained.
  • the azo dye obtained by coupling diazotized p-anisidine to 2,3,3-trimethyl-indolenine is converted into the color base with sodium hydroxide solution and suction filtered.
  • 40.8 g of the moist intermediate 29.3 g of dry color base are heated to 90 ° C. with 40 g of chlorobenzene and 34 g of water for 10 minutes and then cooled to 30 ° C.
  • 40 g of dimethyl sulfate (0.32 mol) are added dropwise at 30 ° C. with gentle cooling.
  • the pH drops to 2.2. With the aid of a metering device controlled by a pH device, the pH is then adjusted to 7 by dropwise addition of 10% sodium hydroxide solution and the mixture is stirred at 30-35 ° C.
  • the precursors obtained by coupling diazotized aniline, 4-toluidine, 2-toluidine, 2-anisidine, 3-chloro-4-anisidine and 4-phenetidine to 2,3,3-trimethylindolenine are used , and otherwise proceeds in the same way, you also get valuable cationic hydrazone dyes.
  • 33 g of the intermediate which is obtained by coupling diazotized 4-anisidine to 2,3,3-trimethylindolenine in hydrochloric acid solution, are mixed with 10 g of chlorobenzene, 75 g of water in which 1 g of the adduct of 10 mol of ethylene oxide and 1 mol of nonylphenol had been dissolved, and 5 g of magnesium oxide were stirred.
  • the color salt is converted into the base.
  • 44 g of dimethyl sulfate are added dropwise at 25 ° C. with gentle cooling at pH 9.5; the pH is then 8.6. After stirring for 5 hours at 25 ° C., the pH drops to 2.4. Another 1 g of magnesium oxide is added, the mixture is stirred at 25 ° C.
  • the equimolecular amounts of the color salts which are obtained by coupling diazotized aniline, 4-toluidine and 4-phenetidine, to 2,3,3-trimethyl-indolenine, 5-chloro-2,3,3 -trimethyl-indolenine, 2,3,3,5-tetramethyl-indolenine and 5-methoxy-2,3,3-trimethylindolenine, and otherwise proceeds in the same way, so you also get valuable cationic hydrazone dyes.
  • the mixture is stirred for a further 60 min, the temperature being allowed to rise to 40 ° C. by reducing the cooling and stirring continued at this temperature.
  • the pH value is initially between 7.5-8.5, after the addition of dimethyl sulfate it drops to 6.5-6.7 and then slowly rises again to 7.0.
  • the stirrer is now switched off for phase separation.
  • the yellowish aqueous phase which is slightly clouded by undissolved magnesium oxide, quickly settles down.
  • the organic phase is dark red and clear.
  • the aqueous phase is separated off, the aqueous dichloropropane phase remains in the reaction vessel.
  • the dye-containing dichloropropane phase settles out as a dark red, clear liquid, it is separated and evaporated and dried in a thin-film evaporator or in a vacuum paddle dryer at a temperature of 60 ° C. 215 g of a cationic hydrazone dye with a precursor content of less than 0.1% are obtained.
  • indolenine color salts which are obtained by coupling aniline, 4-toluidine, 2-toluidine, 2-anisidine, 4-phenetidine and 3-chloro-4-anisidine to 2,3, 3-trimethyl-indolenine, 2,3,3,5-tetramethyl-indolenine, 2,3,3-trimethyl-5-methoxy-indolenine, 2,3,3-trimethyl-5-ethoxy-indolenine, 2,3, 3-Trimethyl-7-methoxy-indolenine, 2,3,3-trimethyl-5-chloro-indolenine and 2,3,3-trimethyl-5-chloro-7-methoxy-indolenine can be obtained, and otherwise proceeds in the same way , you also get valuable cationic hydrazone dyes.
  • the mixture is stirred for about 1 h until the crystals begin to form, and 40 g of water are then added dropwise at 40-50 ° C. in the course of 1 h.
  • the temperature is then kept at 40-50 ° C. for a further 5 h, then heated to 60 ° C. in 1 h and the temperature is kept at 60 ° C. for a further 60 min.
  • the preliminary product content in the finished methylated dye is below 0.1%.
  • 100 ml of water are now added and the mixture is stirred at 60 ° C. for a further 15 min; the pH of the mixture adjusts to 6.0-6.5.
  • the stirrer is switched off for phase separation.
  • the lower aqueous phase is separated off.
  • 220 g of the cationic hydrazone dye are obtained with a Intermediate product content of less than 0.1%.
  • indolenine color salts are used, which are obtained by coupling aniline, 4-toluidine, 2-anisidine and 3-chloro-4-anisidine to 2,3,3-trimethylindolenine, 2,3, 3,5-tetramethyl-indolenine, 2,3,3-trimethyl-5-methoxy-indolenine, 2,3,3-trimethyl-5-ethoxy-indolenine, 2,3,3-trimethyl-7-methoxy-indolenine, 2,3,3-trimethyl-5-chloro-indolenine and 2,3,3-trimethyl-5-chloro-7-methoxy-indolenine are obtained, and otherwise the same procedure is followed, so that valuable cationic hydrazone dyes are also obtained.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Coloring (AREA)
  • Indole Compounds (AREA)
EP80104329A 1979-08-04 1980-07-23 Verfahren zur Herstellung kationischer Farbstoffe Expired EP0023671B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19792931687 DE2931687A1 (de) 1979-08-04 1979-08-04 Verfahren zur herstellung kationischer farbstoffe
DE2931687 1979-08-04

Publications (2)

Publication Number Publication Date
EP0023671A1 EP0023671A1 (de) 1981-02-11
EP0023671B1 true EP0023671B1 (de) 1982-02-03

Family

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Family Applications (1)

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EP80104329A Expired EP0023671B1 (de) 1979-08-04 1980-07-23 Verfahren zur Herstellung kationischer Farbstoffe

Country Status (6)

Country Link
US (1) US4281112A (es)
EP (1) EP0023671B1 (es)
JP (1) JPS5624451A (es)
BR (1) BR8004858A (es)
DE (2) DE2931687A1 (es)
ES (1) ES493959A0 (es)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2945028A1 (de) * 1979-11-08 1981-05-21 Hoechst Ag, 6000 Frankfurt Quartaere und basische azamethinverbindungen, verfahren zu ihrer herstellung und ihre verwendung als farbmittel
DE3013273A1 (de) * 1980-04-05 1981-10-08 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung kationischer farbstoffe
DE3013272A1 (de) * 1980-04-05 1981-10-08 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung kationischer farbstoffe
JPS5728049A (en) * 1980-06-11 1982-02-15 Ciba Geigy Ag Manufacture of carbinol base from indoline compound
US4925926A (en) * 1986-12-15 1990-05-15 Ciba-Geigy Corporation Preparation of cationic azo or hydrazone dyes in which the alkylation and the separation of the cationic dye are carried out continuously
JPH0297209A (ja) * 1988-09-30 1990-04-09 Fujitsu General Ltd 同軸ケーブル端末の加工方法
CN113861719B (zh) * 2021-09-30 2023-10-17 浙江闰土染料有限公司 一种阳离子黄的清洁制备方法

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH363749A (de) * 1957-08-30 1962-08-15 Bayer Ag Verfahren zur Herstellung von Farbstoffen
BE570686A (es) * 1957-08-30
DE1205638B (de) * 1960-04-22 1965-11-25 Basf Ag Verfahren zur Herstellung basischer Farbstoffe
CH515310A (de) * 1968-07-03 1971-11-15 Bayer Ag Verfahren zur Herstellung basischer Farbstoffe
US3741982A (en) * 1969-09-03 1973-06-26 Mitsubishi Chem Ind Novel basic, cationic dyestuff
DE2031202C3 (de) * 1970-06-24 1979-01-04 Bayer Ag, 5090 Leverkusen Hydrazonfarbstoffe, Verfahren zu deren Herstellung und ihre Verwendung zum Färben und Bedrucken von Polyacrylnitril, Vinylidencyanid, sauer modifizierten Polyester- und Polyamidfasern, Leder, taiuiierter Baumwolle, ligninhaltigen Fasern, Schreibflüssigkeiten und Druckpasten
DE2040872C3 (de) * 1970-08-18 1978-04-20 Bayer Ag, 5090 Leverkusen Hydrazonfarbstoffe
DE2060614C3 (de) * 1970-12-09 1980-06-19 Bayer Ag, 5090 Leverkusen 9a-Methyl-23,9,9a-tetrahydro- oxazolo- [3,2,-a] indole
JPS526740B2 (es) * 1973-05-09 1977-02-24
JPS5543022B2 (es) * 1973-06-19 1980-11-04
DE2340571C3 (de) * 1973-08-10 1982-01-21 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von heterocyclischen Verbindungen
US3973903A (en) * 1974-03-05 1976-08-10 E. I. Du Pont De Nemours And Co. Azomethine dye solutions
DE2452321A1 (de) * 1974-11-05 1976-05-06 Basf Ag Basische farbstoffe
DE2506444A1 (de) * 1975-02-15 1976-08-26 Bayer Ag Herstellung von loesungen basischer farbstoffe
US4026885A (en) * 1975-05-13 1977-05-31 Ciba-Geigy Corporation Process for the manufacture of cationic hydrazone dyes
GB1512753A (en) * 1977-01-19 1978-06-01 Yorkshire Chemicals Ltd Hydrazone basic dyes

Also Published As

Publication number Publication date
DE2931687A1 (de) 1981-02-26
EP0023671A1 (de) 1981-02-11
BR8004858A (pt) 1981-02-10
JPS5624451A (en) 1981-03-09
ES8105364A1 (es) 1981-05-16
DE3060179D1 (en) 1982-03-11
US4281112A (en) 1981-07-28
ES493959A0 (es) 1981-05-16

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